Disazo dye and process of making same.



UNITED STATES Parent @FFMJE.

PAUL J ULIUS, OF LUDWIGSHAFEN-ON-'lHlll-RMINE, GEBJAANY, ASHGN QR T BADISOHE ANILIN AND SQDA. FABRIK, OF Lii'DWlGSl-IAFEN(TN-THE- RHINE; GERMAN-Y, A CORPORATION OF GERMAN Y.

olsAzo DYE AND Psoosss or MAKBNG sates.

SIiE GIFIQATION forming part of Letters Patent No. 716,242, dated December 1902.

1 5 prod uct,and suitablycombining the so-formed diazo compound with beta naphthol. In

I place of the 1-naphthylamin-6-sulfo-acid abovementioned there may be employed 1- naphthylan infi-sulfo-acid, or a mixture of both acids, 'suchas is obtained in manufacturing operations, all of which sulfo-acids are to be hereinafterunderstood as being included in the generic term Oleves alphanaphthylamin-monosulfo-acid.

.2 5 The para-chlor-ortho-amidosalicylic acid above mentioned has hitherto not been prepared. A method of obtaining the same is hereinafter given.

i The disazo dye above mentioned dyes wool from an acid-bath aviolet-black @0101, which on treatment with bichro nate of potash turns black.

' In the following thenature of this inven tion is illustrated by means of examples; but the invention is not limited to the proper tions and conditions therein given. The parts are by weight, and the temperaturedegrees refer to the centigradescale- Example l-P'roduction of para-chz'or-salt 4o ct Zia amide-Suspend one hundred and thirty eight (138) parts of salicylic. acid in seven l1undred (700) parts of nitro-benzene and pass into it seventy-one (71) parts of chlorin, maintaining the temperature during this operation atfroin fifty to sixty (),degrees and agitating well the meanwhile. Extractthe parachlor-salicylic acid from the nitro-benzone by means of a dilute. aqueous solution of carbonate of soda, and from thesewatery ex 5o tract-s precipitate the free para-chlor-salicylic 'Baum hydrometer.

Applioation'filed December 23, 1901. Serial No. 87,001. iSpecimena.)

acid'by means of hydrochloric acid. The crude product so obtained usually carries more than ninety (00) per cent. oi the pure para-chlor-salicylic acid.

Erample Z--Pmduction of Mirachlor-sali- 3 5 cylz'o ac2'(l.--Dissol ve three hundred and fortyfour (345i) parts of para-chlor-salicylic acidin sixteen hundred (1,000) parts of sulfuric acid containing ninety-six per cent; of sulfuric acid (H SOQ at a temperature of from thirty 60 (30) to forty (40) degrees. New cool the whole to a temperature ranging from five degrees below zero (-5) to zero degrees and add to it a mixture of two hundred and eighteen (218) parts of nitric acid containing sixty two ((52) per cent. of nitric acid (HN'O and two hundred and eighteen (218) parts of sulfuric-acid containing, one hundred percent.

of sulfuric acid (H SO (so-called monohydrate,) stirring the meanwhile, care being p taken that during this operation the temperature of the mixtures does not rise above zero degrees. Stir until a test carriedlout by means of the Lungs nitrometer shows that nitration is practically completed. This is usually effected in from three .(3) to four (4) hours. "When nitration is practically com pleted, pour the result upon about two thousand (2,000) parts of ice, collect the acid in any suitable manner, such as filtration and subsequent pressing.

.Emcwnpie 3-Pro(Zuct/lon of para-c711 or-orthoamide-salicylic CLCZ'CZ.7FOI. this it is recommended to employ the moist press-cake resulting from Example 2. Take three hundred and seventy-five (375) parts of nitro-paracblor-salicylic acid ora corresponding amount of moist press-cake and stir it up with fivehundred (500) parts of Water and add a saturated solution of carbonate of soda until evo- 9o lution of gas ceases. Now add two thousand and seven hundred (2,700) parts of a solution of bisulfite-ot' soda registering about 40 0n a Heat this result to boiling under a return-condenser and maintain it so for from one and a-hali to three hours. Now add twelve hundred (1,200) parts of hydrochloric acid containing about thirtythree (33) per cent. of hydrochloric acid. (H01) and boil. until the sulfurous acid has been expelled. The new chlor-amido-salicylic acid is now present partially in solution (probably as hydrochloric acid salt) and partly as undissolved 'free acid. The free acid may be obtained from the hydrochloricacid salt by careful addition of carbonate of soda. This new chlor-amido-salicylic acid, which occurs in fiat needles, can also be obtained by careful addition of hydrochloric acid to a solution of the sodium salt. The acid is ditticultly soluble in cold water, difficuitly soluble in alcohol, and melts at about two hundred and thirty-six (236) degrees, decomposing at the same time. The sodium salt 'occurs in short needles, is soluble in water, and may be precipitated from this solution by means of common salt.

The hydrochloric-acid salt of this new.chlor-amido-salicylic acid is quite readily soluble in an exboss of hydrochloric acid.

Example .-Produci'z'on 07" the dye parachZor-ortho-amido-saZicyZ'ic acid (1.20 alphanaphih'ylamin-monosuUh-acid-a20-beta-naphih0l.-Dissolve eighteen and seventy five hundredths (lS (one-tenth molecular proportion) parts of para-chlor-ortho-amido-salicylic acid in six hundred (600) parts of hot water and the necessary amount of carbonate of soda. Cool to and add-a concentrated aqueous solution of sodium nitrite containing six and nine-tenths (65 parts of that salt, (one-tenth molecular proportion.) Then add rapidly thirty-five parts of hydrochloric acid containing thirty-three (33) per cent. of hydrochloric acid (HGl) (three-tenths molecular proportion.) The diazotation takes place rapidly. The resulting yellow diazo compound separates out in great part in the form of yellow needles and is introduced into forty.() degrees.

' of the necessary quantity of a solution of twentyfour and five-tenths (24- parts of the sodium salt of Gleves alpha naphthylamin tenth molecular proportion) (preferably the crude acid,whic h is a mixture of l-naphthylamin-G-sulfo-acid and of l-naphthylamin- 7-sulfo-acid) in four hundred (400) parts of water. Stir for about one (1) hour and add thirteen and siX- tenths (13- parts (onetenth molecular proportion) of crystallized sodium acetate. Stir for seven (7) hours while maintaining the temperature at about Let it stand over night. This completes the combination. The next step may be carried out on the result of the preceding operation itself, or the intermediate product may be precipitated from this result by means of about fifty (50) parts ofhydrochloric acid containing thirty-three (33) per cent. of hydrochloric acid (l-ICl) and then filtered off. In either case acomplete solution of the intermediate product is effected by means carbonate of soda, and to this solution thereis added a concentrated aqueous solution of sodium nitrite containingand nine-tenths (6%) parts (one tenth molecular proportion) of that salt. Now add a suilicient quantity of ice and sixty monosulfo acid (one parts of hydrochloric acid containing thirty-three (33) per cent of hydrochloric acid, (H01). Stir for about one-half (4 hour. At the end of that time the diazo compound, which is difficultly. soluble in water, will be formed. Introduce this result into a solution made from sixteen(16) parts of betanaphthol, (about one-tenth molecular proportion), twelve (12) parts of caustic-soda lye containing thirty-five (35) per cent. of caustic soda (NaOH) (one-tenth molecular proportion,) fifty-five (55) parts of calcined carbonate of soda, and five hundred (500) parts of water. Stir for about three (3) hours. The dye will then have separated out completely and can be collected by any suitable means, such as filtering and pressing. The so-resulting product in the dry and powdered stateis a greenish-black powder having a metallic sheen which gives a red-violet solution in cold water, which solution is not affected in color by a small quantity of carbonate of soda. A larger quantity of carbonate of soda, however, produces a brown-red precipitate. Addition of hydrochloric acid to the aqueous solution produces a violet-red precipitate. The dye gives an indigo-blue solution with caustic-soda lye and a dark-blue color with concentrated sulfuric acid. The dye dyes wool aviolet-black shade, which on treatment with bichromate of potash becomes a deep black, which resists the eitect of external in iluences, such as fulling, washing, potting, ironing, and the like. The shades produced are likewise exceedingly level. Y

\Vhat is claimed is 1. Process for the production of an azo dye which consists in treating salicylic acid successively with chlorin, nitric acid, bisulfite of soda, nitrous acid, combining the resulting 'orthodiazoparachlor -salicylic acid with Cieves alpha-naphthylamin-monosulfo-acid, treating the resulting product with nitrous acid and combining the resulting diazo compound with beta-naphthol.

2. Process for which consists in treating para-chlor-salicylic acid successively with nitric acid, bisulfite of soda, nitrous acid, combining the resulting diazo-para-chlor-salicylic acid with Cleves alpha-naphthylamin-rnonosulfo-acid,treating this result with nitrous acid and combining the resulting diazo compound with beta-naphthol.

3. Process for the production of an azo dye which consists in treating ortho-nitro-parachlor-salicylic acid with bisulfite of soda, and then with nitrous acid, combining the resultingortho-diazo-para-chlor-salicylic acid with Cleves alpha-naphthylamin-monosulfo-acid, treating the resulting product with nitrous acid and combining the resulting diazo compound with beta-naphthol.

4. As a new article of manufacture the azo dye which can be obtained by combining diazotized ortho-amido-para'chlor-salicylic acid with Cleves alpha-naphthylamiu-monosulto acid, diazotizingthis product and combining the resulting diazo compound with beta-imply thol, which dyes woolin shades which a re converted into deep black by bichromate of pot-f ash and which is soluble in water giving a red violet color which remains unchanged by smallamounts of carbonate of soda but which solution yields a precipitate with an excess of carbonate of soda and With hydrochloric acid, v

and which dye dissolves in caustic soda with PAUL JULIUS.

Witnesses:

BERXHARD C. HEssE, JACOB ADRIAN. 

